Vat dyestuffs and process of preparing them



Patented Nov. 29, 1932 WILHELM 0mm Ann o'r'ro Bn lnnsnon GERMANY,ASSIGNQRS T0 GENERAL AN A conronnmron or DELAWARE F, or FiannarcnT-o'nrHn-Mziin-Hoo str, rrrnn wons, me, on NEW YORK, n. x,

VAT nvnsrnrrs AND PROCESS or PREPARING THEM No Drawing. Applicationfiled May 29',',1929,"Seria1 No. 367,114, and in Germany June 18, 19 28.

The present invention relates tovat dyestuffs and a process ofpreparing'them.

In U. S Patents No. 1,588, l-51 dated Line 15, 1926, No. 1,690,775 datedNovemberfi, 1928, No. 1,765,661 dated June 24, 1930, and No. 1,765,662dated June 24, 1930, a new class of vat dyestufishas beendisclosed.obtainable by condensing 1.4.5.8-naphthalenetetra-car; boxylic acid orits dianhydride or substitution products thereof with ortho-diamines orsalts thereof in the presence or absence of solvents or diluents. Thesedyestuffsare mixtures, of compounds of the following general a 35 graphof this specification in whichthe aryl wherein R and R stand for anunsubstituted i or substituted arylene. By the said process there can,stuffs in which'R and R represent the same aryl' group in eachderivative'of this class.-

Now We have found that new Vat dyestuffs of the type describedin theopening para other are obtainable by condensing anaphthoylene-aryl-imidazo'l-peri-dicarb0xylic anhydride of'the followinggeneral forniula f N/ I 9 I The condensation is effected by mixing thecourse, likewise be used.

'wherein stands for the; bivalent radical however, be obtained only vatdye- 1 7 1 g .1

gandfR and fora nucleus ofthe group con- 2 sisting" ofbenzene,naphthalene and, ,ac e-' naphthene, which may containsubstituents and is bound intwo adjacent positions to the nitrogen atom,but 5R being difierent from roups R3 andRi are diflerent from oneanlproducts having the constitution of one of the possible lsomers.

' carboxylicacids and anhydrides thereof, re-

wherein R stands fora substituted or unsubstituted aromatic groupboundlnt'wo ad acent positions, with an aromatic ortho-dlam'ine.

components, advantageously in the presence of a solvent such as glacialacetic acid, nitror benzene, ater or the like, and heatlng the reactionmixture. Instead of the above nen- V tioned' peri-dicarboxylic.anhydride the corresponding free carboxylic acids can, of

By the said the following tainable:

process 'newwat dyestutfs 0f. probable formula are obtained as mixturesof isolneric dyestuffs, in 7 other cases they are obtained as uniform pThe new dyestufis dye the cotton fiberfrorn the vat tints of excellentfastness properties.

v The naphthoylene-aryl iinidazol-peri-di spectively, may be obtained,for instance, by theprocess disclosed in our co-pending applicationSerial No. 367,1 18 of even date.

The following examples serve to illustrate our invention but they, arenot intended to, limit it thereto, the parts being by weight: 100

"the process disclosed in our co-pending U. S. I patent application lastreferred to are heated '(1) 3.4 parts ofnaphthoylene-benzimidazol-peri-dicarboxylic acid or itsanhydride,respectively,. obtainable according to to entle boiling with1.4 parts of 1.2-dimet yl-4.5-diamino benzene in about times theirweight of glacial acetic acid and .boilingis continued until theprecipitation of thedyestufi? is finished The reaction takes thefollowing course 'wherein R stands for The dyestufi is filtered withsuction, washed with glacial acetic acid, ethylalcohol and water. It isabrownish-red powder which dissolves in concentrated sulfuric acid to ared solution; It dyes cotton from a greenhydrosulfite vat which has in athick layer and by reflected light a red-appearance, copper-red tints ofgood fastness properties.. 7

naphthoy- When heating 3.4 partsof 'lene-benziinidazol-peri-dicarboxylicacid or its anhydride in about 10 times their weight of glacial aceticacid with Iii-parts of 1.2- diamino-naphthalene, the condensationproduct "separates after a shorttiine as a brown "crystallineprecipitate. It. I is filtered with suction. washed and dried and thus adyestuif :of one of the following probable formulae:

wherein R stands for the bivalent radicals o ot ' wherein R stands forthe saine dyes'tufi" is obtained as by condens- 7 ing 1.L.5.S-naphthalene-tetra-carboxylic acid with ortho-phenylene-d1an11neaccording to the process disclosed in U. S. Patent No. 1,588,451. It hasexactly the same properties as the dyestuffsdescribed in that patent.

(4:) By condensing in the manner described in the preceding erianiples3.4 parts of naphthoylene benziinidazol peri dicar- 'boxylic anhydridewith 1.3 parts of a t-diainidotoluene, a red dyestuff is obtained whlchdyes cotton from an olive green hydrosulhte vat red tints of goodsfastness properties. The reaction proceeds according tothe followingformulae:

wherein R1 stands for i i (5) When starting from the naphthoylene-methylbenzimidazol peridicarb oxylic acid-which can be obtained by treatingaccording to the process described in our c0- pending U. S. applicationlast referred to the condensation thalene-fi-diethyl indandion 4 1.8dicarboxylic anhydride and 3.4-diamino-toluene'and stuff is obtainedhaving the same properties as that described in Example 4:. The reac-jtion takes the following course 70H: V a

N N N V (6) By dispersing partsofnaphthoylene-benzilnidazol-peridicarboxylic anhya dride and 1,6 parts of 1-ethoxy-3/l-a1nin0- benzenein about 1O times their weighflof glacial acetic'acidand heating themixture fiber from an olive product obtainable from naphtreating it withLQ-diamido-ben'zene, a dyeto boiling for some time; the condensationproducttobtained according to the following equation:

. V a v oozes 002m separates as a brown precipitate. stufi, after beingisolated in the usual manner,"is a brown powder and dyes the cottonbrown alkaline hydrosulfite vat brown tints of good'fastness properties. r

" (7) 3.4 parts of naphthoylene-benzimidazol-peri-dicarboxylic anyhride"are heated to gentle'boiling in a'rnixture of 20 parts of nitrobenzeneand the equal quantity of glacial acetic acid and then a solution of 1.5parts 0f- 4-chloro-1.Q-diaminobenzene in glacial acetic acid is added.After a short time the "condensation product obtained racv cording tothefollowing equation:

wherein 'R (stands for is filtered with suction, washedwith glacialacetic acid, ethyl alcohol and Water. The

dyesturf thus 'obtained'is in a dry'statea red line crystalline powderwhich dissolves in The dyep separates as a red crystalline precipitate.It

V 'sulfite vat red brown tints.

benzene and the graycolor turns concentrated v sulfilr'ic acid "to ayellow-red solution and dyes cotton from an olivegreen vat red tints ofgood fastness properties.

By replacing in the reactionprocess described in Example 7 the 4chloro-1L2'-"diamino-benzene by the corresponding quantity of.4-bromo-12-diaminobenzene, a' dyestufi is obtained according to'thefollowing equation: 7. a I I v NHz It dyes-cotton from an'olive greenhydro- Its fastness properties are Very similar to; the chlorinecontaining dyestuifobtained according to Example 7. Y (9) Bycondensingin a, mixtureofnitroglacial acetic acid3.5 parts ofnaphthoylene benzimidazol. peri dicarboX- ylic anhydride with 1.6

represents a mono-nitro-componnd of the dyestuff obtainable bycondensing "124.5.8-

naphthalene-tetra-'carooxylic dianhydride with" l2-dia1nino-benzeneaccording to the processes disclosed in the U.-S.

opening-paragraph of the present application. It dyes the cotton fiberfrom a green hydrosulfite vat intense gray tints of fairly goodfastnessto washing. vOn chlorination brown. .Thedyestuir 1s formed according tothe following'equation:

ing to the following equation:

parts of 4i-nitr'o-l2f V diamino-benzene a dyestuif is obtained whichpatent'speci- I ficationsand applications referred to in the wherein Rstands for (10) By condensingnaphtl1oylene-benzimidazol-peri-dicarboxylic acid or its anhydride with3.4-diannnoacenaphthene according-to the methods described in thepreceding examples a dyestuff is'obtained which dyescotton from an olivegreen hydrosulfite vat covered brown tints of good fastness propertiesThe dyestufi is formed accord- We claim 1. The process which comprisescondensmg a compound of the following formula:

' for hydrogen or methyl,

with an aromatic ortho-diamine of the group consisting of those of thebenzene, naphthalene and-acenaphthene series while heating'inthepresence of an'inert diluent.

series while heating to mg a compound of thefollowing formula:

with an aromatic ortho-diamine of the group consisting of those of thebenzenenaphtha lene and acenaphthene to boiling temperature glacialacetic acid. 7 7 3. The process which comprises condensingnaphthoylene-benzimidazol-peri-dicarboxylic anhydride with an aromaticorthodiamine of the'group consisting of those of the benzene,naphthalene and acenaphthene series while heatingin the presence of aninert diluent. I

4. The process which comprisescondensing naphthoylenebenzimidazol-peri-dicarboxylic'anhydride with an aromatic 0rthodiamineof the group consisting of those of the benzene, naphthalene andacenaphthene boiling temperature glacial acetic acid. 5; The processwhich comprises condensing, naphthoylene-benzimidazol-peri-dicarboxylic.anhydride with an ortho-diamine of the group consisting of those of thenaphthalene and benzene series wherein the benzene nucleus may besubstituted in -position by methyl, ethoxy halogen or the nitro group,while heating in thepresence of an inert diluent.

6. The process which comprises condensseries while heating in thepresence of ing naphthoyleneebenzimidazol-peri dican inethylyethoxyhalogen orlthe'nitro group,

while heating to boiling temperature in the boxylic anhydride with anortho-diamine of the group consisting ofthose of the naphthaleneandfibenzene series whereinthe benzene nucleus may be substituted in4-position by presence of glacial aceticacld. I p

7, The, process which comprises condens- 1n bo ziylic anhydridewith.LQ-diaminO-naphthalene while heating in the presence of an inertdiluent.

8. The process which comprises condensingnaphthoylene-benzimidazol-peri-dicarboxylic anhydride with1.2-diamino-naphthalene while heating to boiling temperature in thepresence of glacial acetic acid.

in the presence of naphthoylene-benzimidazol-peri-dicarfollowingprobable formula:

@L a p wherein R stands for the biyalentji'adical;

v \N/ iv 7 in which R represents'a nucleus of the group consisting ofnaphthalene and benzene which is substituted in t position by methyl,ethoxy, chlorine, bromine or' the nitro group in each case bound in twoadjacent positions to the nitrogen atoms which products are uniformdyestuffs or mixtures of isomeric dyestuffs, dyeing cotton from the vatVery fast tints.

I As a new product, a vat dyestuff of the following probable formula:

I whereinB stands for the bivalent radical:

mula

vat dyestuffs of the following probable for.-

6 wherein standsfor'the bivalent radical:

said product being a-brown powder and dyeing the cotton fiberfrom anolive'brown alkaline: hydrosulfite vat brown tintsof good fastn'essproperties.

-sis

' group 12. As a new product, a mixture of isomeric vat dyestuffs ofthefollowing probable formula:

wherein R stands for the bivalent radical:

N i or Y Br I I 71.31 said product dyeing cotton from an olivegreenhydrosulfite vat red "brown tints.

13. The process which comprises condens mg a compound of the generalstructure:

i,ss9,279

14:. The process which comprises condensing a compound of thegeneral'structure:

wherein R stands for an aryl radical of the group consisting of arylradicals of the benzene, naphthalene and acenaphthene series,

which is bound in two adjacent nuclear positions to the nitrogen atomswith an aromatic 'ortho diamine of the group cons1sting of those of thebenzene, naphthalene and acenaphthene series, while heating to boilingtemperature in the presence of glacial acetic acid. c

15. As new products, the compounds of the probable general structure:

A N\ /N 06 0 wherein R stands for an aryl radical of the groupconsisting of aryl radicals of'the benzene, naphthalene and acenaptheneseries,

which is bound in two adjacent nuclear posltions to the nitrogen atomsand R stands for the bivalent radical 0i i N N I R,

wherein R represents an aryl radical of the group'consisting of arylradicals of the benzene, naphthalene and acenaphthene series, which isbound in two adjacent nuclear positions to the nitrogen atoms, R beingdifierent from R, which products are uniform dyestuiisor mixturesofisomeric dyestufls, dyeing cotton from the vat very fast tints.

In testimonywhereof, we aifiX- our signatures.

' WILHELM ECKERT.

OTTO BRAUNSDORF.

